Stability control of a hydrogen generating system and method

ABSTRACT

A method of and apparatus for efficient on-demand production of H 2  and O 2  from water and heat using environmentally safe metals are disclosed. In one aspect, the apparatus for hydrogen generation through water-decomposition reaction includes a main reactor, an oxidizer reactor, and a computer-control system. The computer system is configured to control each of the components of the hydrogen gas production system for stable hydrogen-gas production.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent applicationSer. No. 12/706,639, filed Feb. 16, 2010, and entitled “Method andApparatus for Efficient On-demand Production of H₂ And O₂ From WaterUsing Waste Heat and Environmentally Safe Metals”, which claims priorityfrom U.S. Provisional Patent Application Ser. No. 61/154,282, filed Feb.20, 2009 and entitled “Method and Apparatus for Efficient On-demandProduction of H₂ And O₂ From Water Using Environmentally Safe Metals”,which are all hereby incorporated herein by reference in their entiretyfor all purposes.

Further, this application claims priority from U.S. Provisional PatentApplication Ser. No. 61/441,193, filed Feb. 9, 2011 and entitled“Stability Control of a Hydrogen Generating System and Method,” which ishereby incorporated herein by reference in its entirety for allpurposes.

FIELD OF THE INVENTION

The present invention relates to the field of hydrogen and oxygenproduction. More specifically, the present invention relates to thefield of on-demand hydrogen and oxygen production from water using heat,water, and environmentally safe catalysts.

BACKGROUND OF THE INVENTION

Hydrogen is commonly produced from hydrocarbon fossil fuels. One of thesignificant problems of using hydrocarbon fossil fuels to generatehydrogen is that the process generates carbon dioxide (CO₂), agreenhouse gas. An alternative source for hydrogen production is water.Currently available methods of generating hydrogen from water includebiological hydrogen production, electrolysis of water, chemicalproduction, and thermochemical production.

Some researchers report that Group IV transitional metals react withwater and generate hydrogen gas and a metal hydroxide. However, theconversion rates of these metals cannot produce large volumes ofhydrogen gas for efficient and practical use. Furthermore, there are noefficient methods or apparatuses available to recycle the metalhydroxides and convert the hydroxide into hydrogen and oxygen.

SUMMARY OF THE INVENTION

Methods and apparatuses for efficient on-demand production of H₂ and O₂from water and heat and/or light using environmentally safe metals aredisclosed. In one aspect, the apparatus for the hydrogen generationthrough water decomposition reaction includes a main reactor, anoxidizer reactor, and a computer-control system.

In some embodiments, the main reactor contains electrodes, reactants,catalysts, and solvents. A voltage is applied to the electrodes forassisting the hydrogen production. The reactants and catalysts of thesystem include a hydrogen-generating substance, water, and salts. Thecatalysts are able to be activated by the electrochemical methods.Hydrogen gas is generated with heat supplied in the main reactor. Afteror during the reaction, the solution in the main reactor flows to theoxidizer reactor for regeneration reactions. In some embodiments, theregeneration reaction liberates O₂ gas.

In some embodiments, the oxidizer reactor is configured for photolysisor thermolysis for an oxygen reaction. In some embodiments, thethermolysis is at a temperature above 32° C. and below 110° C. In someembodiments, the computer-control system controls the operation of thesystem and monitors the status of each reaction reactor andcorresponding reaction conditions. The computer-control system containssoftware to control and monitor reaction conditions, such as pH values,temperature, salinity, applied voltage, catalyst formulation, purity andquantity of the gases generated, water level, color, solution level, andother proper factors.

In the following, some aspects of maintaining a stableelectro-catalytic-hydrolysis system are provided. In an aspect, a methodof maintaining the performance of a catalytro-catalytic-hydrolysissystem comprises preparing the electric-catalytic-hydrolysis systemcomprising a solution containing a hydrogen generating catalyst, a lightproviding device and an electric energy providing device and optimizinghydrogen production by optimizing a reaction condition. In someembodiments, the hydrogen generating catalyst contains an aluminum ion,a copper ion, and a silver ion. In some embodiments, optimizing areaction condition comprises maintaining the pH value below 8.5. Inother embodiments, optimizing a reaction condition comprises maintainingthe reactor core pH value between 7.5 and 8.5. In some otherembodiments, optimizing a reaction condition comprises maintaining thepH value in a range capable of optimizing a hydrogen production rate. Insome embodiments, optimizing a reaction condition comprises optimizingan amount of the hydrogen generating catalyst. In other embodiments,optimizing the amount of the hydrogen generating catalyst comprisesincreasing a regeneration rate of the hydrogen generating catalyst. Insome other embodiments, the regeneration rate of the hydrogen generatingcatalyst comprises a rate of converting a reacted hydrogen generatingcatalyst back to the hydrogen generating catalyst. In some embodiments,optimizing a reaction condition comprises optimizing a regeneration rateof Ag⁰. In other embodiments, optimizing a reaction condition comprisesoptimizing an amount of Ag⁰, Ag¹⁺, or a combination thereof. In someother embodiments, optimizing a reaction condition comprises increasingthe rate of dissociating oxygen from the silver ion. In someembodiments, optimizing a reaction condition comprises increasing therate of dissociating a hydroxide from the silver ion. In otherembodiments, optimizing a reaction condition comprises increasing therate of dissociating a hydroxide from the copper ion. In some otherembodiments, optimizing a reaction condition comprises optimizing alight providing amount through the light providing device. In someembodiments, optimizing a reaction condition comprises optimizing heatproviding duration, a heat providing rate, a heat providing amount, or acombination thereof through a heat providing device. In otherembodiments, optimizing a reaction condition comprises optimizing avoltage providing through the electric energy providing device.

In another aspect, a device for maintaining a performance of a systemcomprises an electro-catalytic-hydrolysis system comprising a solutioncontaining a hydrogen generating catalyst, a light providing device andan electric energy providing device and a controller to control areaction condition such that a hydrogen generation reaction isoptimized. In some embodiments, the hydrogen generating catalystcontains an aluminum ion, a copper ion, and a silver ion. In someembodiments, controlling a reaction condition comprises maintaining thereactor core pH value below 9.7. In other embodiments, controlling areaction condition comprises maintaining the pH value between 7.5 and8.5. In some other embodiments, controlling a reaction conditioncomprises optimizing an amount of the hydrogen generating catalyst. Insome embodiments, controlling a reaction condition comprises increasinga regeneration rate of the hydrogen generating catalyst. In otherembodiments, the regeneration rate of the hydrogen generating catalystcomprises a rate of converting a reacted hydrogen generating catalystback to the hydrogen generating catalyst. In some other embodiments,controlling a reaction condition comprises optimizing a regenerationrate of Ag⁰. In some other embodiments, controlling a reaction conditioncomprises optimizing an amount of Ag⁰, Ag¹⁺, or a combination thereof.In other embodiments, controlling a reaction condition comprisesincreasing the rate of dissociating oxygen from the silver ion. In someother embodiments, controlling a reaction condition comprises increasingthe rate of dissociating a hydroxide from the silver ion. In someembodiments, controlling a reaction condition comprises increasing therate of dissociating a hydroxide from the copper ion. In otherembodiments, controlling a reaction condition comprises optimizing alight providing rate, a light providing amount, a light providingfrequency, or a combination thereof through the light providing device.In some other embodiments, controlling a reaction condition comprisesoptimizing a heat providing rate, a heat providing amount, or acombination thereof through a heat providing device. In someembodiments, controlling a reaction condition comprises optimizing avoltage providing rate, a voltage providing amount, or a combinationthereof through the electric energy providing device.

In a further aspect, a method of controlling anelectric-catalytic-hydrolysis system comprises monitoring a reactioncondition of the electric-catalytic-hydrolysis system and maintainingthe reaction condition in a pre-determined range, such that a catalytichydrogen production reaction is able to generate hydrogen continuously.In some embodiments, the reaction condition comprises a pH value, atemperature, a pressure, an illumination condition, a reactant amount,or a combination thereof. In some embodiments, the illuminationcondition comprises an intensity of illumination. In other embodiments,the illumination condition comprises a duration of illumination. In someother embodiments, the pH value at the oxidizer is between 8.5 and 10.5.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates the components of a system in accordance with someembodiments.

FIGS. 2A and 2B illustrate the generation and regeneration reactions inaccordance with some embodiments.

FIG. 3 illustrates the overall reaction of a system in accordance withsome embodiments.

FIG. 4 illustrates a process of a hydrogen-generation reaction inaccordance with some embodiments.

FIG. 5 illustrates a setup in some accordance with embodiments.

FIG. 6 illustrates an in-situ hydrogen and oxygen production system inaccordance with some embodiments.

FIG. 7 illustrates a method of electric-hydrolysis reaction for hydrogenproduction in accordance with some embodiments.

FIG. 8 a and FIG. 8 b illustrate equations of a hydrogen productionscheme in accordance with some embodiments.

FIG. 9 illustrates a hydrogen production system in accordance with someembodiments.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Illustrative System

FIG. 1 illustrates a system 100 in accordance with some embodiments. Insome embodiments, the apparatus for the hydrogen generation throughwater decomposition includes: a main reactor 102, an oxidizer reactor104, a heat source 108, and a computer-control system 106. In someembodiments, the main reactor 102 is a chamber where hydrogen isgenerated. Further, the main reactor 102 contains electrodes 102A,reactants, catalysts, and solvents. The electrodes 102A contain iron,graphite, stainless steel, alloy, or any other proper materials. In someembodiments, the stainless steel includes Stainless 302, 316, 316L, 421.In some embodiments, the electrodes are metal alloy, such as Fe/Al orFe/Cr/Mn and Fe/Si/Mn alloys. In some embodiments, the alloys have aFe/Al mole or weight ratio of 97/3, 95/5, or 93/7. A voltage is appliedto the electrodes 102A. In some embodiments, the voltage is generated bya power source 102B. In some embodiments, the voltage applied is between0.8V and 3.0V. Alternatively, the voltage applied is about 5V or anyvoltage between 0.2V and 10.0V. In some embodiments, −2.5V or 0V isapplied to a graphite electrode and +1.7V is applied to metal for 15minutes, 1.4V is applied to copper metal for 10 minutes, and 1.0V isapplied to silver metal for 5 minutes when ionizing the metals in thereaction solution. In alternative embodiments, −2.5V is applied to agraphite electrode and +2.5V is applied to aluminium, copper, and silvermetals concurrently for about 30 minutes when ionizing the metals intothe reaction solution. Further, in some embodiments, a voltage between−0.4V and −0.9V is applied to a stainless steel electrode (cathode)during the electric-hydrolysis reactions. It should be understood thatthe voltage range mentioned above is an example, and other possiblevoltages are able to be applied. The reactants and catalysts of thesystem include the hydrogen-generating substance, water, and salts.

In some embodiments, the hydrogen-generating substance contains a metal,a metal oxide, a metal hydroxide, or a metal derivative compound.Alternatively, the hydrogen-generating substance contains an Al atom, Alion, an atom with an atomic number 13, or combinations thereof.Alternatively, the hydrogen-generating substance contains [Al(OH)₄]⁻,Al(OH)₃, [Al(OH)₂]⁺, Al³⁺, or [Al(OH)]²⁺. A person skilled in the artwould appreciate that the hydrogen-generating substance is able tocontain Group IA to VIIA elements, such as magnesium, calcium, silicon,cobalt, and gallium. In some alternative embodiments, thehydrogen-generating substance contains Group IB to VIIB elements, suchas zinc, nickel, iron, and copper. Alternatively, thehydrogen-generating substance contains inner transitional elements. Aperson of ordinary skill in the art would appreciate that other suitablechemical elements, alloys, nanomaterials, polymers, and natural orsynthetic compounds are able to be used. Further, a person skilled inthe art would appreciate that the terms “bind,” “binding,” “bound,” orfunctionally equivalent terms are examples of showing that two or moresubstances have interactions or forces between or among them. Thepresent disclosure is not limited to actually binding, bonding, orforming chemical bonds.

In some embodiments, the water used has a salinity of about 1.5% byweight. Other suitable percentages of salinity are able to be used, suchas sea water, which has salinity about 3.8%. The salts used are able toinclude NaCl (sodium chloride), CaCl₂ (calcium chloride), Na₂CO₃, orother suitable ion sources. The gases generated, such as hydrogen, aretransferred through the pipe 102C. After or during the reaction, thesolution in the main reactor 102 flows to the oxidizer reactor 104 foroxygen reactions.

In some embodiments, the oxidizer reactor 104 is configured forphotolysis or thermolysis for the oxygen-liberation reactions. The lightsource 104A generates light for the photolysis reaction. A heat source(not shown in the figure) generates heat for thermolysis. In someembodiments, the temperature for the thermolysis reaction is less than200° C. In other embodiments, the temperature for the thermolysisreaction is equal to or above 200° C. In some embodiments, the heatsource transfers and/or collects environmental heat to be used by thesystem 100. The gases generated are transferred through the pipe 104C. Aperson skilled in the art would appreciate that other proper methods orapparatuses are able to be used for the oxygen reaction.

In some embodiments, the heat source for electro-catalytic-hydrolysis isable to be an independent heat exchanger 108. A person skilled in theart will also appreciate that the heat source is able to be installed inthe main reactor 102 or in any other suitable chambers.

In some embodiments, the computer-controller 106 controls the operationsof the system 100 and monitors the status of the reaction conditions ineach of the reaction reactors. The computer-controller 106 contains acontrol software application 106A to control and monitor reactionconditions, such as pH value, temperature, salinity, applied voltage,purity and quantity of the gases generated, water level, catalystformulation, catalyst reaction characteristics, and solution level inthe main reactor 102 and the oxidizer reactor 104. A person skilled inthe art would appreciate that the computer-controller 106 is able to beused for other purposes, including controlling and adjusting thereaction conditions.

A person skilled in the art would appreciate that the above stated setupis one of the examples. Other proper setups are able to be applied tothe system. For example, the reaction reactors 102 and 104 are able tobe combined into a single reactor. Additional reaction reactors are ableto be added.

Reactions

In some embodiments, a system uses the following reactions to generatehydrogen by decomposing water: (1) REDOX reaction, (2) pre-generationreaction, (3) generation reaction, (4) regeneration reaction, (5) secondhydrogen reaction, and (6) oxygen reaction.

(1) REDOX Reaction

The REDOX reaction prepares a prehydrogen-generating substance byoxidizing or reducing the starting materials. Subsequently, thehydrogen-generating substance reacts with water or hydroxide. The REDOXreaction is illustrated in equation (1). Equation (2) illustrates thatthe prehydrogen-generating substance reacts with water to form thehydrogen-generating substance. A person skilled in the art willappreciate that the hydrogen-generating substance is able to carry acertain amount of surrounding water in its surrounding sphere.

$\begin{matrix}{M->{M^{x +} + {xe}^{-}}} & (1) \\{{M^{x +} + {y\; H_{2}O}}->{\left\lbrack {M({OH})}_{y} \right\rbrack^{x - y} + {\frac{y}{2}H_{2}}}} & (2)\end{matrix}$

In the equations (1) and (2), M and its ion form represent the core ofthe hydrogen-generating substance and x and y represent chargeparameters for an oxidation state or reaction stoichiometry.

A person of ordinary skill in the art will appreciate that the REDOXreaction is one exemplary model, and the starting material is notrequired to go through the REDOX reaction to become an active catalystand/or a hydrogen-generating substance for the hydrogen generation. Insome embodiments, the hydrogen-generating substance is the precursor ofthe actual hydrogen-generating catalysts, which generate hydrogen gas.Alternatively, the hydrogen-generating substance is thehydrogen-generating catalyst, and the starting material is the precursorof the hydrogen-generating substance.

(2) Pre-Generation Reaction

In some embodiments, the pre-generation reaction is a step of setting upthe AID (Active Ion Displacement) condition for the generation reaction.The pre-generation reaction applies a minimum starting voltage (eg. 0.5VDC) to the electrodes in the solution that contains thehydrogen-generating substance. The pre-generation reaction makes thehydrogen-generating substance, such as [Al(OH)₃.xH₂O] complex, compactonto/couple with the Fe electrode surface. The pre-generation reactionis a process that requires a low energy potential. In some embodiments,it is observed that the pH of the solution is raised during thepre-generation reaction, and it is able to result from the liberation ofthe OH⁻ groups to the solution.

(3) Generation Reactions

In some embodiments, the generation reaction generates hydrogen anddepletes the hydrogen-generating substance. For example, when thehydrogen-generating substance is [Al(OH)₃], the generation reactiongenerates hydrogen gas and produces a depleted hydrogen-generatingsubstance, [Al(OH)₄]⁻. The substance [Al(OH)₃] is used herein as anexample. The hydrogen-generating substance is also able to be [M(OH)₄]⁻,[M(OH)₃], [M(OH)₂]⁺, [M(OH)]²⁺, M³⁺, or other suitable chemicals thatare able to perform similar reactions as described above.

Active Ion Displacement (AID)

In some embodiments, the generation reaction is achieved by an activeion displacement (AID) reaction. The chemical reaction of the AID isillustrated in equation (3).

$\begin{matrix}{{{2\left\lbrack {{M({OH})}_{y} \cdot {z\left( {H_{2}O} \right)}} \right\rbrack}^{p - y}\overset{{AID}\text{-}{reaction}}{\longrightarrow}{2\left\lbrack {{{M({OH})}_{y + 1} \cdot \left( {z - 1} \right)}\left( {H_{2}O} \right)} \right\rbrack}^{p - y - 1}} + H_{2}} & (3)\end{matrix}$In the equation (3), [M(OH)_(y).z(H₂O)]^(p-y) is the chemical state ofthe hydrogen-generating substance before the generation reaction. Zrepresents the number of water molecules surrounding the core of thehydrogen-generating substance. P—Y represents the charges of thehydrogen-generating substance binding with y equivalents of hydroxide. Yrepresents the number of hydroxides binding to the hydrogen-generatingsubstance before the AID reaction. Through the AID reaction, the[M(OH)_(y).z(H₂O)]^(p-y), with the assistance of applied electriccharge, becomes [M(OH)_(y+1).(z−1)(H₂O)]^(p-y−1). Equation (3) is anexample that illustrates the concept of the invention. For example, the[M(OH)_(y).z(H₂O)]^(p-y) is able to be [Al(OH)₃.x(H₂O)] and the[M(OH)_(y+1).(z−1)(H₂O)]^(p-y−1) is able to be [Al(OH)₄.(x−1)(H₂O)]⁻. Aperson skilled in the art would appreciate that the hydrogen-generatingsubstance is also able to be in other chemical states, contain any othersuitable number of hydroxide groups, or contain other suitable ligands.In some embodiments, external heat aids the AID reaction.

The AID reaction is able to reduce water and associate the OH⁻ groupwith the hydrogen-generating substance. The AID reaction is furtherillustrated in equation (4), where [Al(OH)₃.x(H₂O)] is used as anexample of the hydrogen-generating substance. The x equivalent of watersurrounding the core of the hydrogen-generating substance is used as anexample. In some embodiments, the hydrogen-generating substance is ableto use the water in the solution directly.

$\begin{matrix}{{\left\lbrack {{{Al}({OH})}_{3} \cdot {x\left( {H_{2}O} \right)}} \right\rbrack\overset{AID}{\longrightarrow}\left\lbrack {{{{Al}({OH})}_{4} \cdot \left( {x - 1} \right)}\left( {H_{2}O} \right)} \right\rbrack^{-}} + {{1/2}H_{2}}} & (4)\end{matrix}$

FIG. 2A shows the reaction between the hydrogen-generating substance 208and the water molecules 212. In some embodiments of the AID reactions,the hydrogen-generating substance 208 is [Al(OH)₃.x(H₂O)], which reactswith the water molecules 212 and generates protons (H⁺) 216 or hydrogen214. The AID reactions are able to be assisted by an applied voltagepotential to the electrode 202. These mechanisms are described as merelyexamples. A person skilled in the art would appreciate that the hydrogengas is able to be generated through a hydride and a proton or any othersuitable way of generating hydrogen gas. The hydrides and protonsdescribed in this disclosure are able to bind to the hydrogen-generatingsubstance, be generated by the hydrogen-generating substance, and bindto other compounds in the solution. It is known by a person skilled inthe art that amphoteric properties of aluminum hydroxides are able toadd efficiency to the AID reaction of the generation reaction. It isobserved that the pH of the solution is increased during the AIDreaction, and it is able to be caused by the hydroxide generation orliberation in the AID reaction. In some embodiments, the pH value isable to be controlled by the concentration of Catalyst Base Formulation(CBF) fluid flow rate through the Reactor Core and Oxydizer. In someembodiments, the CBF is the hydrogen generation substance.

A person skilled in the art would also appreciate that thehydrogen-generating substance is able to generate hydrogen throughprotons, hydrides, or combinations thereof by a single molecule or bythe cooperation of multi-molecules or atoms, such as alloys and aplurality of the same or different metal centers.

(4) Regeneration Reactions

In some embodiments, the regeneration reaction regenerates thehydrogen-generating substance from the depleted hydrogen-generatingsubstance. For example, the [Al(OH)₄.(x−1)(H₂O)]⁻ is able to beregenerated back to [Al(OH)₃.x(H₂O)] or to [Al(OH)₃.(x−1)(H₂O)].

The generation reaction and the regeneration reactions make the wholereaction work in a catalytic manner until the hydrogen-generatingsubstance converts to a less active or another stable state (unusablecompound).

The chemical equation of the regeneration reaction is illustrated inequation (5).[¹M(OH⁻)_(y)]+²M^(+x)→[¹M(OH⁻)_(y-z)]+[²M^(+x)(OH⁻)_(z)]  (5)In the equation (5), [¹M(OH⁻)_(y)] is the depleted hydrogen-generatingsubstance, and ²M^(+x) is a regenerating substance. The regenerationreaction strips or liberates the hydroxide group bonded to the depletedhydrogen-generating substance, so the hydrogen-generating substanceregenerates from the state of depleted form, [¹M(OH⁻)_(y)], directly orindirectly back to the previous chemical state, such as [¹M(OH⁻)_(y-z)].The ²M^(+x) is acting as a hydroxide shuttle, such as Ag, Ag(OH), Cu,and Cu(OH)⁺¹, that removes or carries the hydroxide group from thedepleted hydrogen-generating substance. The above equation is an exampleto illustrate the concept of this disclosure. A person skilled in theart would appreciate that the hydrogen-generating substance is able tobe in other oxidation states, contain any other suitable number ofhydroxide groups, or contain other suitable ligands.

The regeneration reaction is able to dissociate the OH⁻ group away fromthe hydrogen-generating substance to which OH⁻ originally bonds. Theregeneration reaction is illustrated in equations (6) and (7) using[Al(OH)₄.(x−1)(H₂O)]⁻ as the example of the depleted hydrogen-generatingsubstance. A person skilled in the art will appreciate that theregeneration reaction is also able to occur between Ag(OH)_(r) andCu(OH)_(r), which are able to act as the hydroxide shuttle for eachother. R represents the numbers of hydroxides that are associated withthe core of the hydroxide shuttle, and the value of R is able to be 0,1, 2, or any other suitable number.

$\begin{matrix}{{2\left\lbrack {{{{Al}({OH})}_{4} \cdot \left( {x - 1} \right)}\left( {H_{2}O} \right)} \right\rbrack}^{-} + {{Cu}^{2 +}\overset{Regeneration}{\longrightarrow}{2\left\lbrack {{{{Al}({OH})}_{3} \cdot \left( {x - 1} \right)}\left( {H_{2}O} \right)} \right\rbrack}} + {{Cu}({OH})}_{2}} & (6) \\{{2\left\lbrack {{{{Al}({OH})}_{4} \cdot \left( {x - 1} \right)}\left( {H_{2}O} \right)} \right\rbrack}^{-} + {{Ag}^{2 +}\overset{Regeneration}{\longrightarrow}{2\left\lbrack {{{{Al}({OH})}_{3} \cdot \left( {x - 1} \right)}\left( {H_{2}O} \right)} \right\rbrack}} + {{Ag}({OH})}_{2}} & (7)\end{matrix}$

FIG. 2B illustrates a regeneration reaction in accordance with someembodiments. The hydrogen-generating substance 208 binds the hydroxidegroup 206. The hydroxide shuttles 203, 204, or 210 are able to take thehydroxide group 206 away from the depleted hydrogen-generating substance208. The hydroxide shuttle is able to be a silver ion 204, a copper ion210, an aluminum ion (not shown in the figure), multi-ion centeraggregation 203, or other chemicals that take up the hydroxide group206.

The term “regeneration reaction” includes any reactions that revive thedepleted hydrogen-generating substance back to the hydrogen-generatingsubstance that is active as a catalyst for assisting the electrichydrolysis. The term “hydroxide shuttle” is used as an illustration ofthe present invention, and the hydroxide shuttle is able to include anystructure to remove any chemical substance from the hydrogen-generatingsubstance. As such, the hydroxide shuttle is not limited to removingonly hydroxyl groups. The hydroxide shuttle is able to act as a shuttleto remove hydrides, hydrogen, or other substances that bind to orassociate with the hydrogen-generating substance.

(5) Second Hydrogen Reaction

In some embodiments, the generation reaction produces a depletedhydrogen-generating substance, which is bonded with the additionalhydroxide group. The regeneration reaction uses hydroxide shuttles totake the hydroxide group from the depleted hydrogen-generatingsubstance. After taking the hydroxide group from the depletedhydrogen-generating substance, the hydroxide shuttle bonds with thehydroxide group. Subsequently, the second hydrogen reaction converts thehydroxide group bonded on the hydroxide shuttle into hydrogen proton/gasand metal oxide. For example, Ag²⁺ or Ag⁺ takes hydroxide from[Al(OH)₄.(x−1)(H₂O)]⁻ and becomes Ag(OH)₂ or Ag(OH) through theregeneration reaction. The second hydrogen reaction converts Ag(OH)₂into AgO and/or Ag₂O and hydrogen. In some embodiments, theabove-mentioned reactions occur in the main reactor (e.g., reactor 102in FIG. 1).

(6) Oxygen Reaction

In the oxygen reaction, the oxygen of the metal oxide, which isgenerated in the second hydrogen reaction, is released from the metaloxide through photolysis, thermal decomposition, or other suitablechemical reactions or physical interactions. Through the oxygenreaction, the hydroxide shuttle is regenerated, and the hydroxideshuttle is able to take hydroxide from the depleted hydrogen-generatingsubstance or other hydroxide shuttle having bonded hydroxide again. Forexample, the silver ion is regenerated from silver oxide (AgO) throughan oxygen reaction. In some embodiments, the energy source of thephotolysis for the oxygen reaction is visible light, UV waves,microwaves, radio frequency waves, gamma rays, x-rays, IR waves, or anyother type of energy that a person skilled in the art would appreciate.In some embodiments, the metals that can be used as the hydroxideshuttle include aluminium, alumina, copper, iron, silver, zinc,magnesium, gallium, nickel, or any other metal or nonmetal material orcompounds that are capable of taking up hydroxide groups. The metal ionmentioned above is able to be in various oxidation states. For example,a silver ion is able to be Ag metal, Ag⁺, Ag²⁺ or Ag³⁺.

A person skilled in the art would appreciate that the oxygen reaction isable to be performed with heat, light, or other suitable energy sources.Further, a person skilled in the art will appreciate that the secondhydrogen reaction and the oxygen reaction are able to be part of thehydrogen-generating reactions, and the so-called hydroxide shuttles areable to be part of the hydrogen-generating substance.

Overall Reactions

FIG. 3 illustrates an overall reaction cycle 300 in accordance with someembodiments. The reaction begins with an aluminium (Al) metal 302.Through the REDOX reaction, the Al metal 302 becomes Al³⁺ 304.Alternatively, the aluminium ion 304 is generated from other sources ofAl ion such as bauxite, Na[Al(OH)₄], Al(OH)₃, NaAlO₂, Na₂AlO₄, Na₅AlO₄,NaAl₁₁O₁₇, or any other suitable Al ion sources. The Al ion 304 reactswith water (H₂O) 306, generating hydrogen gas 308 and thehydrogen-generating substance, aluminium hydroxide [Al(OH)₃.x(H₂O)] 310.With the assistance of AID prepared hydrogen producing substrate afterthe pre-generation phasing, the hydrogen-generating substance 310 reactswith two surrounding water molecule. Hydrogen gas is generated in thegeneration reaction and the hydrogen-generating substance becomes adepleted hydrogen-generating substance, [Al(OH)₄.(x−1)(H₂O)]⁻, 312. Theregeneration reaction removes one OH⁻ ion from [Al(OH)₄.(x−1)(H₂O)]⁻312; thus, the depleted hydrogen-generating substance,[Al(OH)₄.(x−1)(H₂O)]⁻, 312 becomes the substance [Al(OH)₃.(x−1)(H₂O)]314. Subsequently, the [Al(OH)₃.(x−1)(H₂O)] 314 associates with waterand turns back into [Al(OH)₃.x(H₂O)] 310. Through the generation andregeneration reactions, the hydrogen-generating substance works in acatalytic manner.

In some embodiments, the regeneration reaction uses a copper ion 332 ora silver ion 352 as the hydroxide shuttle. The copper ion 332 and thesilver ion 352 are able to be generated through REDOX reactions frommetal copper 330 and silver 350 or prepared from other suitable ionsources. The hydroxide shuttles take up the hydroxide groups 316 andbecome a hydroxide-bonded hydroxide shuttle, such as Cu(OH)₂ 334 orAg(OH)₂ 354. A person skilled in the art will appreciate that thehydroxide shuttle is able to be in various oxidation states and bondedwith various numbers of hydroxides 316.

In some embodiments, the second hydrogen reaction generates morehydrogen and converts the hydroxide-bonded hydroxide shuttle, such asAg(OH)₂ 354, into a metal oxide, such as AgO 356, or a silver ion.

In some embodiments, the oxygen reaction generates oxygen 358 and renewsthe metal oxide, such as AgO 356, into a renewed hydroxide shuttle.Through the second hydrogen reaction and the oxygen reaction, thehydroxide shuttles work in a catalytic manner.

FIG. 4 further illustrates a process of the electrically controlledhydrogen-generation reaction 400 in accordance with some embodiments.The process begins with preparing the starting material 402. At the step404, the hydrogen-generating substance is prepared by the REDOXreaction. At the step 405, the hydrogen-generating substance reacts withwater and becomes active hydrogen-generating substance.

At the step 406, the generation reaction makes the hydrogen-generatingsubstance react with water or intramolecular hydrolysis reaction throughan applied voltage potential to produce hydrogen gas viaelectric-hydrolysis reactions. The hydrogen-generating substance becomesa depleted hydrogen-generating substance. At the step 408, theregeneration reactions use hydroxide shuttles to regenerate the depletedhydrogen-generating substance. At the step 410, the second hydrogenreaction and the oxygen reactions revive the hydroxide shuttle. At thestep 412, the hydrogen-generating substance is regenerated. After thestep 412 the process goes back to the step 405, and the whole reactionworks in a catalytic manner.

A person skilled in the art will appreciate that the above process ismerely one example. All steps are optional and additional steps are ableto be added. Further, the reactions are able to go through othermechanisms.

EXPERIMENTS Example 1

In some embodiments, an apparatus includes a main reactor, aphotochemical/oxidizer reactor, and a thermal source. The main reactorcore contains reactants or catalysts, graphite and stainless steelplates as electrodes. The photochemical/oxidizer reactor contains anenergy source or an energy converter, such as a light source, a sunlightreceiver capable of transforming sunlight in other forms, a solar waterheater, or other proper lights or heaters.

The conditions and procedures of performing the reactions are describedin detail below. The experiment begins with a catalyst preparationprocedure. In the catalyst preparation procedure, water, salts, and thestarting metals, including substrates of Al, Cu, and Ag, are placed intoa catalyst preparation vessel. Next, the starting materials are preparedby using the REDOX reaction, which is described in the followingparagraph. Subsequently, the product of the catalysts preparationreaction is transferred to the main reactor. The main reactor containswater, such as water prepared from tap water, distilled water, deionizedwater, or sea water. The salts are added to bring the salinity of thewater to at least 1.5% using a refractometer by weight using NaCl.

In the REDOX reactions, the electricity is applied to the electrodes. Anegative charge is connected to the graphite electrodes and a positivecharge is connected to copper, silver, and aluminum electrodes. Thereactions are started by applying a voltage sufficient large (e.g., 1.8volts) to cause the Al, Cu, and Ag substrate to begin to liberate gas.The reactions are run for 30-40 minutes or until a gel suspension orheavy and frothy supernatant is developed. The solution is stirredoccasionally until the supernatant completely dissolves into solutionand forms a gelatinous suspension.

Following the catalysts preparation is the pre-generation reaction. Inthe pre-generation reaction, the anode in the main reactor (thestainless steel electrode) is conditioned for AID. In some embodiments,the temperature of the reaction is set in the range from 80° F. to 185°F. The negative charge of applied electricity is connected to thestainless steel electrode and the positive charge is connected to thegraphite electrode. Before applying an electric voltage, the Cu, Al, andAg metals are taken out of the solution. Next, 0.3V of electricity isapplied. After the current is stabilized, the voltage is applied inincrements of 0.01V until the voltage is roughly 0.4V or until H₂ gas isproduced at the stainless steel substrate. In some embodiments, it isobserved that the pH value of the solution increases quickly during thepre-generation reaction.

Following pre-generation phasing reaction, the generation reaction isperformed. In the generation reaction, the voltage is initiated at 0.1Vand increased by 0.05V increments, such as 0.105V, 0.110V, and 0.115V.The voltage is continuously increased up to approximately 0.820 volts oruntil the maximum amount of the gas is generated. During this phase,hydrogen gas is produced at the stainless steel substrate. Then thevoltage is reduced by 0.05V until the gas production falls off.

The hydrogen gas in the above setup is produced from the stainless steelelectrode. It is observed that during the reaction, the pH value quicklyincreases. After the reaction, the pH value decreases to about 6.5 aftera period of about 12 hours (overnight) if the applied voltage potentialis turned off.

In some embodiments of this renewable catalytic system, the reactionbegins with 0.22 g of Al, 0.060 g of copper and 0.017 g of silver metalsto produce five liters of gas.

After the above reactions, the hydrogen-generating substance isdepleted, leaving in the main reactor a solution that contains thedepleted hydrogen-generating substance and hydroxides-bonded hydroxideshuttles. The solution is transferred from the main reactor to theoxidizer reactor for oxygen reaction to revive the hydroxide-bondedhydroxide shuttles and hydrogen-generating substance. The gelatinoussuspension contains the reactivated hydrogen-generating substance, andthe solution containing the gelatinous suspension is then transferredback to the main reactor. The oxidizer reactor is able to be aphotochemical reactor or the thermal converter. The oxidizer reactor isturned on when the pH value of the reacting solution increases. In someembodiments, the oxidizer reactor is turned on at all times.

Example 2

FIG. 5 illustrates a system 500 in accordance with some embodiments. Theapparatus 500 includes a preparation reactor 503, a main reactor 514, aphotochemical/oxidizer reactor 532, and a thermal converter 530.

In some embodiments, the experiments are performed as follows. Thereaction begins with preparing a solution 501 containing 250 mg of Al502 metal, 50 mg of Cu 504 metal, 25 mg of Ag 506 metal, a graphiteelectrode 512 and 1 liter of water 508 having 1.5% NaCl 510 by weight. Anegative voltage of −1.7V is applied to the graphite electrode 512 and apositive is applied to the Al metal 502 for 15 minutes. Next, the firstpositive voltage applied to the Al metal 502 is removed, and a secondpositive voltage of 1.4V is applied to the Cu metal 504 for 10 minuteswhile the negative voltage of −2.5V is applied to the graphite electrode512. Next, the second positive voltage is removed from the Cu metal 504,and a third positive voltage of 1.0V is applied to the Ag metal 506 for5 minutes with the negative voltage still applied to the graphiteelectrode 512. The temperature of the solution is maintained at 88° F.In some embodiments, the procedures that are described above includeionizing the metals into the solution. In some embodiments, theprocedures are for catalysts preparation.

Next, the solution 501 is transferred to the main reaction vessel 514.The main reaction vessel 514 contains aluminium ions 515, copper ions517, silver ions 520, sodium ions 522, and chloride ions 524. The term“ion” comprises all ligand states of a metal. For example, an aluminiumion includes Al³⁺ or Al(OH)_(x), where the x represents the coordinatedligand numbers of the aluminium ion. In some embodiments, a voltagebetween 0.4V and 0.9V is applied to the cathode of the electrodes. Inalternative embodiments, a voltage of 0.85V is applied to the cathode ofthe electrodes. In other embodiments, a voltage not exceeding 0.9V isapplied to the cathode of the electrodes, because some experimentsindicate that hydrogen production is reduced when a voltage exceeding0.9V is applied. In some embodiments, the applied voltage of the anodeis at 0V compared with a voltage on the standard hydrogen electrode. Inalternative embodiments, the anode of the electrode is the referenceelectrode, which has a voltage of 0V. In some embodiments, the voltageis applied in a way that a negative charge is applied to the stainlesssteel electrode 516 and a positive charge is applied to the graphiteelectrode 518. A hydrolysis reaction begins to occur when sufficientvoltage is applied, and hydrogen gas 536 is generated at the stainlesssteel electrode 516 when the voltage is applied to the stainless steelelectrode 516 and the graphite electrode 518. After 30 minutes or whenthe amount of hydrogen gas production begins to decrease, the solutionin the vessel 514 is transferred through the heater 530 and passed underthe LED lights 532 to produce a photolysis reaction. Oxygen gas 540 iscollected at the outlet 538 during the photolysis reaction. The solutionis transferred back to the main reaction vessel 514 for hydrogenproduction.

In some embodiments, a control system 534 is connected to all thecomponents of the system 500, including the preparation vessel 503, themain reaction vessel 514, valves 526, the heater 530 and/or heatexchanger, the LED lights 532, and all the electrodes 502, 504, 506,512, 516, 518. In some embodiments, the control system 534 comprises oneor more computers, which are able to automate the control of each of thecomponents of the system 500. Accordingly, the control system 534 isable to automate the whole electric-hydrolysis process whenpredetermined conditions have been reached. For example, the controlsystem 534 is able to initiate the reaction automatically by applying avoltage to the preparation vessel 503 when hydrogen gas is needed. Thecontrol system 534 is able to stop the ionization process of the metalsautomatically when a preset condition has been reached, such as, apreset pH value or an applied voltage. Similarly, the control system 534is able to transfer the solution 501 automatically to the variouschambers or vessels by controlling the pump 528 and the valves 526.

The control system 534 is able to control the system 500 remotely. Forexample, the system 500 is able to be controlled through a website, overthe Internet or using a telephone or PDA. In some embodiments, all ofthe processes of the system 500 are able to be all automated, triggeredby at the occurrence of predetermined conditions, such as by using apreset timer or indicator of low fuel of a car.

FIG. 6 illustrates an in-situ hydrogen and oxygen production system 600in accordance with some embodiments. In operation, the system 600 isable to include the system 500 for in-situ and on-demand hydrogen andoxygen production. The hydrogen and oxygen gas produced is able to gothrough the same or independent channels 604 to an internal combustionengine 602, which is able to be installed on a car. The water generatedthrough the hydrogen and oxygen combustion reaction can be recycled backto be used again in the system 500.

The in-situ hydrogen and oxygen production system 600 is able to providefuels, hydrogen gas, and oxygen gas on-demand. Accordingly, the system600 is able to eliminate or replace the need of having high pressurehydrogen gas stored on a vehicle. As a result, the danger of a highpressure storing/distribution device explosion is able to be eliminatedor avoided.

FIG. 7 illustrates a method of electric-catalytic-hydrolysis reaction700 for hydrogen production in accordance with some embodiments. Themethod begins at the step 702. At a step 704, aluminum, copper, andsilver are ionized into a water solution, forming a hydrogen-generatingcatalyst. At a step 706, the solution is maintained at approximately 90°F. At a step 708, a voltage, between −0.4 and −0.9 volts, is applied tothe solution or the cathode of the electrodes, thereby generatinghydrogen gas. At a step 710, the catalytic ability of thehydrogen-generating substance is regenerated by reacting with a firstcatalyst-reviving substance. At a step 712, the first catalyst-revivingsubstance is regenerated by reacting with a second catalyst-revivingsubstance. At a step 714, the second catalyst-reviving substance isregenerated by exposing it to a light, such as green LED lights. Themethod 700 ends at a step 716.

In the following paragraphs, methods of controlling and maintaining astable hydrogen production system in accordance with some embodimentsare provided. FIGS. 8 a and 8 b illustrate equations of ahydrogen-production scheme in accordance with some embodiments.Referring to FIG. 8 a, in equation 802, under the influence of AID,Al(OH)₃ reacts with water forming [Al(OH)₄]⁻ and a proton (H⁺). Next,the hydroxide (OH⁻) of the [Al(OH)₄]⁻ is removed by the AgCu(OH)₂ or anyother compounds and also by conditions, such as cooling, that arecapable of removing the Off. As shown in equation 804, AgCu(OH)₂ removesthe hydroxide (OH⁻) from Al(OH)₄ ⁻, so that the [Al(OH)₄]⁻ is convertedback to Al(OH)₃, which is able to react with water molecules again. Insome embodiments, the silver changes its valence, so that the silver isable to be oxidized from a zero (0) to +1 charge. A person of ordinaryskill in the art would appreciate that the silver is able to be oxidizedto +1, +2, and/or +3 charges and carry 1, 2, and/or 3 hydroxide groups(OH⁻), respectively. The protons in the solution are able to acceptelectrons and form hydrogen gas, which is able to be removed from thesolution for collection, to be used as fuel. In equation 806, the silverhydroxide, Ag(OH), is able to be converted to silver oxide (Ag₂O) andwater. In equation 808, light energy, such as LED, and/or heat is ableto be used to convert the silver oxide (Ag₂O) into silver(0) and oxygengas.

FIG. 8 b provides an alternative hydrogen production scheme inaccordance with some embodiments. The silver chemistry described in FIG.8 b is able to be catalytic reactions that produce hydrogen gas.Alternatively, the silver chemistry described in FIG. 8 b is able to bepart of chemical reactions that work in conjunction with the chemicalreactions described in FIG. 8 a and/or other chemical reactions toproduce hydrogen gas. In Equation 820, Ag⁰ reacts with water to producehydrogen gas, Ag⁺, and OH⁻. In some embodiments, the Ag⁰ reacts withwater at the stainless steel substrate, giving off two electrons to theAID layer and providing 2H⁺ protons for producing hydrogen gas. Theoxidation reaction of Ag is able to go up to various oxidation states,such as +1, +2, +3, or any other oxidation states that Ag can reach. InEquation 822, OH⁻ is able to associate with Ag⁺ to generate Ag₂O andH₂O. In Equation 824, the Ag₂O is able to be reduced to become Ag⁰. Thechemical reactions described herein are in accordance with someembodiments. Any other chemical reactions that are capable of producinghydrogen gas are applicable, so long as the chemical reactions arewithin the scope of the disclosure.

FIG. 9 illustrates a hydrogen production system in accordance with someembodiments. FIG. 9 is able to be read together with the chemicalreactions described in the FIGS. 8 a and 8 b and their associated texts.As shown in FIG. 9, a solution containing Al(OH)₃, AgCu(OH)₂, water andNaCl is able to be transported into a core chamber 902. The core chamber902 is able to function in a way similar to the main reactor 102 (FIG.1). The solution containing Al(OH)₃, AgCu(OH)₂, water, and NaCl is ableto be prepared from starting materials, such as Al metal, Cu metal, Agmetal and salt water. Alternatively, the solution is able to be receivedfrom other chambers and can contain chemicals regenerated from[Al(OH)₄]⁻ and Ag₂O. The equations 802, 804, 820 and 822 (FIGS. 8 a and8 b) are able to occur and hydrogen gas is able to be produced in thecore chamber 902. Next, the solution is able to be transported to anaccumulator chamber 904 and/or an oxygen chamber 906. The solution thatis transported to the accumulator chamber 904 is able to contain[Al(OH)₄]⁻, Cu(OH)₂, Ag⁺, or a combination thereof. In some embodiments,the solution is able to contain at least one substance, such as silverion complex [Ag(OH⁻)_(x)] or copper ion [Cu(OH⁻)_(x)] complex, that iscapable of taking at least one hydroxide (OH⁻) group from the aluminiumion complex, which is used to produce hydrogen gas. With the OH⁻removing mechanism, the aluminium ion becomes active again and iscapable of producing protons and hydrogen gas. The subscript “x”mentioned above denotes the number of hydroxide groups complexed withthe metal ions. The number “x” is able to start from 0, to 1, 2, 3 . . .etc. The accumulator chamber 904 is optional. The equations 806, 808,822 and 824 are able to occur in the accumulator chamber 904, the oxygenchamber 906, or a combination thereof. The accumulator chamber 904and/or the oxygen chamber 906 are able to function similarly to theoxidizer reactor 104 (FIG. 1) and/or the heat source 108 (FIG. 1)described above. With the assistance of the light or heat energy, thesilver oxide (Ag₂O) is able to oxidize the oxygen (O²⁻) atom of the Ag₂Oto become oxygen gas (O₂) and reduce the silver ion of the Ag₂O, such asAg⁺ to Ag⁰, so that the Ag⁰ is able to be used as the hydroxide groupreceiver/remover, which is able to be used to remove at least one OH⁻group from [Al(OH)]⁻ ₄ or a substance that is generated after thehydrogen-production reaction.

In some embodiments, the progress of the chemical reactions in thevarious chambers disclosed herein are controlled by a computer system,which is able to be similar to the computer-control system 106 ofFIG. 1. In some experiments, it is found that hydrogen gas is producedif the pH value in the main core chamber (reactor core chamber) 902 ismaintained in the range of 7.0-8.5, and the hydrogen-gas production isceased if the pH value in the main core chamber 902 is higher than 9.7or 10.5. Accordingly, methods of controlling a hydrogen gas productionsystem are provided herein for maintaining a stable hydrogen gasproduction system. For example, the methods are able to use the computersystem to control and ensure that the pH value in the chambers is in apredetermined range, such as a pH range between 8.4 and 9.5. A person ofordinary skill in the art would appreciate that any other pH ranges areable to be used, so long as the system is able to provide a continuousand/or stable production of hydrogen gas. The methods are able to beperformed by controlling the intensity, wavelength, time, power, or acombination thereof of the illumination. With the control of theillumination, such as by increasing/decreasing the intensity of theillumination, the efficiency and rate of the hydrogen gas production areable to be controlled and/or optimized. In alternative embodiments, themethods of controlling the hydrogen gas production are able to becontrolled by controlling the regeneration of at least one of thehydrogen producing substances, such as regenerating Ag₂O to Ag⁰. In someembodiments, the control of the Ag⁰ concentration in the system andregeneration rate/efficiency is able to be one of the controllingfactors to maintain or optimize the hydrogen gas production describedherein. Similarly, the systems and methods disclosed herein are able touse the computer system to control/automate the control system to ensurea stable hydrogen production system by maintaining the reactions tooccur in a steady state, a dynamic equilibrium, and/or narrowedoperating conditions, such as within predetermined temperature ranges,lighting conditions, and activation voltages.

As described above, some embodiments of the present invention are ableto include the following chemical reactions: a REDOX reaction, apre-generation reaction, a generation reaction, a regeneration reaction,a second hydrogen reaction, and an oxygen reaction. Alternatively, someembodiments are able to include the following chemical reactions: acatalyst preparation reaction, a hydrogen generation reaction, acatalyst regeneration reaction, and a regeneration reaction toregenerate the catalyst regeneration substance.

It has been observed that the pH value of the catalytic system droppedbelow 7.0-6.5 or to slightly acidic levels when the system is shut downovernight. This is able to be resulted from the conversion of the freeOH⁻ that remained in the solution by Al(OH)²⁺.

In some embodiments, it is found that the lack of chloride ions (Cl⁻) inthe reaction solution can result in preventing a complete pre-generationphasing reaction from occurring which in turn prevents generationreactions and the production of hydrogen. This is evidenced when sodiumcarbonate (Na₂CO₃) is substituted for sodium chloride (NaCl_((aq))) orsea water.

Selected Experiments Results

In some experiments, the H₂ production rate falls off from 20 ml/min to2 ml/min after several hours of operation. The reactor is drained andplaced in a cool dry place to let the catalyst settle overnight. Thenext morning, or whenever the system is started up again, it is foundthat the reaction immediately starts back up with high hydrogenproduction rates. Again, the hydrogen production rate falls off over aperiod of time during operation. This indicates that a regenerationreaction is able to be a result of the thermal collapse. It is alsofound that the pH of the catalyst base is about 10 to 11.5 at the end ofthe testing. Overnight, the pH dropped to roughly 6.5 to 7.2.

In another experiment, it was found that the presence of light is ableto reduce the required catalyst activation voltage and current to almost0. In some experiments, a microscopic analysis of sediment precipitateswas performed. The analysis showed that distinctive Ag micro silverycrystalline precipitates are generated at the bottom of the reactorcore, tubes, and other vessels when the catalyst base formulation havingAg (in the form of AgO) is present in the solution and little or nocopper (in the form of copper hydroxide) is in solution. In the casewith a nearly equal molarity of Ag:Cu, no crystals are formed and ashift in color of the catalyst formulation from brownish to blood red isobserved.

Catalyst Formulation:

In some experiments, the catalyst formulation contains 500 mg/liter ofaluminum, 150 mg/liter of copper, and 75 mg/liter of silver at atemperature of 130° F.

Experiment 1

In some experiments, the Hydrogen Production Unit (HPU) ran at 10-20 mlper minute. The pH tested at a location after the reactor core was high,between 7.8-10, and the pH increases to 10-11.7 after the Oxidizerchamber (Oxy). It is observed that the catalyst base showed blood redand nearly opaque. The temperature was held at 130° F. When theactivation voltage was held between 140 and 155 mV, the H₂ flow rateremained stable at 11-20 ml/min, the pH of HPU remained stabilized atabout 8.0, and the pH of Oxy was about 10.5. When the activation voltagewas held between 250 and 300 mV, the H₂ flow rate decreased to 3-5ml/min, the pH value of HPU increased and became stabilized at about9.5, and the pH value of the Oxy was at about 11.3. When the activationvoltage was held between 400 and 850 mV, the H₂ flow rate decreased to2-3 ml/min, the pH value of HPU quickly increased and became stabilizedat about 10.5, and the pH value of the Oxy was at about 11.7. It wasobserved that the laser diodes used were operating at about 30%capacity. The laser diode used was a 1 W, class 4, green 525 nmwavelength diode.

Experiment 2

In some experiments, there were times that hydrogen production peakedfor 2-3 minutes and then came down immediately. An H₂ flow rate between50 ml/min and 200 ml/min was detected. The flow rate decreased and ittook about another 20 minutes to get H₂ peak production again. This isable to result from the breaking loose of the Ag₂O precipitation fromwhere it accumulated. Subsequently the reaction is able to run in anusual condition again.

Experiment 3

In some experiments, the Oxy was upgraded to increase the surface areaand radiation opportunity. The intensity of the light source wasincreased from ten units of 100 mW laser diodes described above to a 100watt incandescent bulb. The result was a consistent 15 ml/min (an 800%increase) in hydrogen flow rate. The H₂ flow rate still fell off over alonger period of time and came back in intermittent spurts.

This increase in H₂ flow rate is able to result from the increase inoxidizer efficiency by increasing illumination. On inspection of the HPUcomponents, a grayish and whitish silty precipitate was found on thefloor of the reactor core, in the fluid lines to the accumulator, on theaccumulator floor, and in the lines to the oxidizer. This silt wasplaced into an Erlenmeyer flask and placed on a window sill. Over time,water vapor formed around the neck and eventually the silt disappeared.

Experiment 4

In some experiments, hydrogen chloride (HCl) was substituted for NaCl inthe formation of the catalyst base. The result showed that an increasein hydrogen production rate was not in stoichiometric relation to theamount of HCl added.

Experiment 5

In some experiments, sodium hydroxide (NaOH) was substituted for NaCl inthe formation of the catalyst base. The result showed an inability tocomplete pre-generation phase.

Observations:

As Ag concentration increases, overall pH of the system decreases. Whenthe Ag concentration is greater than the concentration of Cu(OH)₂, Agbegins to precipitate as a metal. This is able to result from the lackof Cu(OH)₂ available to amalgamate with the Ag metal. Cooling of thefluid exiting the reactor core resulted in the increase of pH, which isable to result from an amphoteric reaction with Al(OH)⁴⁻¹ complexes,which liberates OH⁻. This is able to trigger an Ag reaction:2Ag⁺²+2OH⁻→Ag₂O+H₂O.

A trend is observed that a lower activation voltage (e.g., 150-155 mV)is able to result in higher flow rates than flow rates that aregenerated when using a higher activation voltage (e.g., 250 mV). It isobserved that the activation voltage is inversely proportional to the H₂flow rate. In addition, as the activation voltage increased, the pH ofboth Reactor Core and Oxy increased. The lower the pH in the ReactorCore (pH<8.0), the higher the H₂ flow rate (AID reaction rate).

Some factors are able to be used to improve the efficiency of thehydrogen production, including: adding Reactor Core Graphite Hats toimprove parallel surface reactions, increasing the reacting surface area(e.g., using radial substrates), improving the recovery of stray Ag₂Ofrom Oxidizer (e.g., precipitate recovery), and streamlining the flow offluid through substrates to maximize the transfer of Ag₂O.

A low activation voltage (e.g., 150 mV) is able to ionize Ag to Ag⁺¹.Such a low activation voltage still has the potential to convert Agdirectly or indirectly to Ag₂O compounds. Higher activation voltages(e.g., higher than 250 mV) are able to cause the system to be unstablein the H₂ production rate and higher unfavorable pH values. This is ableto result from the formation of Ag⁺², leading to the formation of AgO,which needs further time to break down into Ag₂O. Accordingly, thehydrogen production efficiency of the system is able to be controlledand optimized by adjusting the conversion from AgO to Ag₂O, which isable to be part of the rate determination step (r.d.s.) of the hydrogenproduction system.

In the oxidizer, Ag₂O is able to be decomposed to react with copperhydroxide complex to form AgCu(OH)₂ amalgam and ½ O₂. Ag Cu(OH)₂ is thentransported to the reactor core's hydrogen-producing substrate, whichpulls a selected number of electrons from the AgO metal (depending onactivation voltage) to create an Ag+1, +2, or +3 ion. Ag^(+x) ions reactwith free hydroxide ions (liberated from the amphoteric-thermal collapseof the Al(OH)₄₊₁ in the fluid in a downstream location of the reactorcore) to eventually reduce to Ag₂O, AgO, Ag₂O₃. The cycle is able tooccur repeatedly.

In some embodiments, the activation voltage is set to 150 mV, causingthe metal amalgam to create Ag⁺¹ ions. One equivalent of Al(OH)₄₊₁complex is able to liberate one OH⁻ group, which is able to be used togenerate Ag₂O. In other embodiments, the activation voltage is set to250 mV, causing the metal amalgam to create Ag⁺² ions. Two equivalentsof Al(OH)₄₊₁ complexes are able to generate two equivalents of OH⁻groups, which are able to result in AgO. In some other embodiments, theactivation voltage is set to 400+mV causing the metal amalgam to createAg⁺³ ions. Three equivalents of Al(OH)₄₊₁ complexes are able to generatethree equivalents of OH⁻ groups, which are able to be used to generateAg₂O₃.

Some functional factors are able to contribute to the stability of theActive Ion Displacement process including: (1) substances transportedfrom Oxy to Core—the system is adjusted to have AgCu(OH)₂ complex ableto move from the oxidizer into the reactor core in order to convert theAg metal into the specified valance; (2) reaction time for the reactionsolution between Core to Oxy—sufficient reaction time is given to formAg₂O complexes between the reactor core substrates and the Oxidizer; (3)Oxy efficiency—the oxidizer is illuminated, and the amount of Ag₂Ocomplexes are reduced, forming AgCu(OH)₂ complexes, which then need tobe transported into the reactor core; (4) Core buildup—the system isable to be designed to transport Ag₂O into Core, which was notdecomposed in the Oxidizer; (5) Ag₂O transit buildup—Ag₂O is able tobuild up (e.g., between the Core, Accumulator, and the Oxidizer) and theflow is able to be optimized to keep the precipitates moving; and (6)AID surface reaction area—the galvanic interaction distances are able tobe optimized to maximize the AID surface reaction area.

Some factors are able to be used to improve the stability of thehydrogen production system. The factors include (1) ensuring one-wayflow of the reactor core fluids, (2) ensuring that thesubstances/precipitants in reactor core have been transported from thereactor core to the oxidizer, (3) ensuring a sufficient flow, so thatthe precipitate does not build up in any part of the pipes. (This factoris related to turbulence management and downward-looking connections),(4) ensuring that there is enough surface area in the vicinity of thelaser exposure, (5) ensuring that there is a delayed process flow fromthe reactor core to the oxidizer (accumulator) in order to react theAg^(+x) ions completely with the OH⁻ groups, (6) collapsing thetemperature downstream from the Core to maximize the amphoteric changeof Al(OH)⁴⁻¹ complex due to the thermal collapse of the fluid, (7)ensuring that the reactor core substrates have parallel galvanicinteractions on both the top and bottom of the reactor core substrates,which is able to maximize reactor core active sites on the surfaces, and(8) finding silver chemistry's pH equilibrium for various complexes ofsilver, to optimize pH for optimal operation of the system.

More factors are able to affect the stability of the reactions. In someembodiments, fluid transportation rates (fluid moving rates) are able toaffect the hydrogen production reaction. It is observed that a fluidflow optimized rate in the reactor core (e.g., the hydrogen productionchamber) past the hydrogen producing substance is between 25% and 50% ofthe velocity of a hydrogen bubble moving through the fluid to thesurface. In some embodiments, the hydrogen bubbling rate is 3inch/second. Accordingly, one of the optimized rate fortransporting/moving the fluid components in the hydrogen productionreactor is between 0.75 inch/second and 1.5 inch/second. It is possiblethat such fluid moving rates provide an ideal generation reactioncondition allowing the exhausted hydrogen generation substance to reactand be removed from the site while maintaining but not sweeping away theprepared pregeneration phasing surface barrier. In some embodiments, thepore size of the honeycomb structure (substrate/electrode) is able toaffect the hydrogen production rate. In some experiments, it is foundthat the pore size between ⅜ inch and 1/16 inch is an ideal size. Insome embodiments, the pore size is ⅛ inch. The size of the pore is ableto affect the flow rate of the fluid within the substrates/electrodes.Accordingly, the pore size of the substrate, the flow rate of the fluid,or a combination thereof is the controlling factor that affects the rateand stability of the hydrogen production reaction. An automatic systemand/or computer-assisted system are able to be configured to monitor andcontrol the above factors to provide a stable/suitable hydrogenproduction system.

The embodiments disclosed in this disclosure provide apparatuses for andmethods of on-demand hydrogen and oxygen production. Further, reactantsand catalysts used in this disclosure are environmentally sustainableand safe materials. Such advantageous features are able to be applied invarious fields, such as fuel technology, renewable energy, batteries,food production, petrochemical, cement, and car industries.

Optimization of the hydrogen generation reaction includes maintainingthe continuously running of the hydrogen production reaction and theelectric-catalytic-hydrolysis system, increasing the turnover-rate orturn-over number of the catalysts, having a higher hydrogen productionrate and/or amount in a given time period, increasing the stability ofthe electric-catalytic-hydrolysis system, and reducing energy/materialsrequired for the hydrogen production. A person of ordinary skill in theart appreciates that optimization includes adjusting any reactionconditions (such as lighting, temperature, sequences and timing oftransporting reaction components among reaction chambers), so that thehydrogen production/generation is able to sustain and continuously run.A person of ordinary skill in the art appreciates that anyphysical/chemical factors are able to be varied as part of reactioncondition adjustment or optimization including intensity, duration,rate, efficiency, amount, and a combination thereof. For example, anapplied lighting intensity is able to be adjusted concurrently withapplied lighting duration so that the generation of hydrogen gasefficiency is optimized to optimal condition.

The metal ions, such as an aluminum ion, a copper ion, and a silver ion,referred herein include metal ions in any charge states and associatewith any anions. For example, aluminum ion is able to be Al³⁺ or Al⁴⁺charges and in the form of Al(OH)₄ ⁻, Al(OH)₃, Al(OH)₂ ⁺, Al(OAc)(OH).

All the steps that are contained in the methods/procedures describedabove are merely illustrative of the principles of the invention. Allthe steps are optional and all the steps, when applicable, are able tobe performed in different sequences as desired. Additional steps arealso able to be added when a person skilled in the art deems proper.

The present invention has been described in terms of specificembodiments incorporating details to facilitate the understanding ofprinciples of construction and operation of the invention. Suchreference herein to specific embodiments and details thereof is notintended to limit the scope of the invention. It will be readilyapparent to one skilled in the art that other various modifications maybe made in the embodiment chosen for illustration without departing fromthe spirit and scope of the invention.

What is claimed is:
 1. A method of maintaining a performance of anelectric-catalytic-hydrolysis system comprising: a. preparing theelectric-catalytic-hydrolysis system comprising a reactor core and anoxidizer reactor, wherein a basic solution is maintained within thereactor core and contains a hydrogen generating catalyst, wherein thehydrogen generating catalyst contains an aluminum complex, a coppercomplex, and a silver complex; b. optimizing hydrogen production bymaintaining a pH value of the basic solution in the reactor core below9.5; and c. regenerating the silver complex by photolysis utilizing alight providing device within the oxidizer reactor.
 2. The method ofclaim 1, wherein the optimizing hydrogen production comprisesmaintaining the of the basic solution in the reactor core pH value below8.5.
 3. The method of claim 1, wherein the optimizing hydrogenproduction comprises maintaining the pH value of the basic solution inthe oxidizer reactor below
 11. 4. The method of claim 1, wherein theoptimizing hydrogen production comprises optimizing an amount of thehydrogen generating catalyst.
 5. The method of claim 4, whereinoptimizing the amount of the hydrogen generating catalyst comprisesincreasing a regeneration rate of the hydrogen generating catalyst. 6.The method of claim 5, wherein the regeneration rate of the hydrogengenerating catalyst comprises a rate of converting a reacted hydrogengenerating catalyst back to the hydrogen generating catalyst.
 7. Themethod of claim 1, wherein optimizing the hydrogen production comprisesoptimizing a regeneration rate of an Ag⁰.
 8. The method of claim 1,wherein optimizing the hydrogen production comprises optimizing anamount of an Ag⁰, an Ag¹⁺, or a combination thereof.
 9. The method ofclaim 1, wherein optimizing the hydrogen production comprises increasingthe rate of dissociating oxygen from the silver complex within theoxidizer reactor.
 10. The method of claim 1, wherein optimizing thehydrogen production comprises converting a hydroxide of a hydroxidecontaining compound into an oxide of a metal oxide.
 11. The method ofclaim 1, wherein optimizing the hydrogen production comprises increasingthe rate of dissociating a hydroxide from the copper complex.
 12. Themethod of claim 1, wherein regenerating the silver complex by photolysiscomprises optimizing light providing duration, a light providingintensity, or a light providing frequency, a combination thereof throughthe light providing device.
 13. The method of claim 1, whereinoptimizing the hydrogen production comprises optimizing a voltageproviding amount, a current providing amount, or a combination thereofthrough the electric energy providing device.
 14. A method ofmaintaining a performance of an electric-catalytic-hydrolysis systemcomprising: a. preparing the electric-catalytic-hydrolysis systemcomprising a reactor core and an oxidizer reactor, wherein a basicsolution is maintained within the reactor core and contains a hydrogengenerating catalyst, wherein the hydrogen generating catalyst containsan aluminum complex, a copper complex, and a silver complex; b.optimizing hydrogen production by maintaining a pH value of the basicsolution in the reactor core below 9.5; and c. regenerating the silvercomplex by thermolysis utilizing a heat providing device after thereactor core.
 15. The method of claim 14, wherein the optimizinghydrogen production comprises maintaining the pH value of the basicsolution in the reactor core below 8.5.
 16. The method of claim 14,wherein the optimizing hydrogen production comprises maintaining the pHvalue of the basic solution in the oxidizer reactor below
 11. 17. Themethod of claim 14, wherein the optimizing hydrogen production comprisesoptimizing an amount of the hydrogen generating catalyst.
 18. The methodof claim 14, wherein optimizing the amount of the hydrogen generatingcatalyst comprises increasing a regeneration rate of the hydrogengenerating catalyst.
 19. The method of claim 14, wherein theregeneration rate of the hydrogen generating catalyst comprises a rateof converting a reacted hydrogen generating catalyst back to thehydrogen generating catalyst.
 20. The method of claim 14, whereinoptimizing the hydrogen production comprises optimizing a regenerationrate of an Ag⁰.
 21. The method of claim 14, wherein optimizing thehydrogen production comprises optimizing an amount of an Ag₀, an Ag¹⁺,or a combination thereof.
 22. The method of claim 14, wherein optimizingthe hydrogen production comprises increasing the rate of dissociatingoxygen from the silver complex within the oxidizer reactor.
 23. Themethod of claim 14, wherein optimizing the hydrogen production comprisesconverting a hydroxide of a hydroxide containing compound into an oxideof a metal oxide.
 24. The method of claim 14, wherein optimizing thehydrogen production comprises increasing the rate of dissociating ahydroxide from the copper complex.
 25. The method of claim 14, whereinregenerating the silver complex by thermolysis comprises optimizing aheat providing duration, a heat providing amount, or a combinationthereof through the heat providing device.
 26. The method of claim 14,wherein optimizing the hydrogen production comprises optimizing avoltage providing amount, a current providing amount, or a combinationthereof through an electric energy providing device.